materials
Article
Corrosion Resistance of AISI 316L Stainless Steel Biomaterial
after Plasma Immersion Ion Implantation of Nitrogen
Viera Zatkalíková 1, * , Juraj Halanda 2 , Dušan Vaňa 2 , Milan Uhríčik 1 , Lenka Markovičová 1 , Milan Štrbák 1
and Lenka Kuchariková 1






Citation: Zatkalíková, V.; Halanda, J.;
Vaňa, D.; Uhríčik, M.; Markovičová,
L.; Štrbák, M.; Kuchariková, L.
Corrosion Resistance of AISI 316L
Stainless Steel Biomaterial after
Plasma Immersion Ion Implantation
of Nitrogen. Materials 2021, 14, 6790.
https://doi.org/10.3390/ma14226790
Academic Editor: Tomasz Lipiński
Received: 4 October 2021
Accepted: 5 November 2021
Published: 10 November 2021
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with regard to jurisdictional claims in
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iations.
Copyright: © 2021 by the authors.
Licensee MDPI, Basel, Switzerland.
This article is an open access article
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Attribution (CC BY) license (https://
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4.0/).
Materials 2021, 14, 6790. https://doi.org/10.3390/ma14226790
1 Department of Materials Engineering, Faculty of Mechanical Engineering, University of Žilina,
Univerzitná 8215/1, 010 26 Žilina, Slovakia; milan.uhricik@fstroj.uniza.sk (M.U.);
lenka.markovicova@fstroj.uniza.sk (L.M.); milan.strbak@fstroj.uniza.sk (M.Š.);
lenka.kucharikova@fstroj.uniza.sk (L.K.)
2 Faculty of Materials Science and Technology, Advanced Technologies Research Institute,
Slovak University of Technology in Bratislava, Jána Bottu Č. 2781/25, 917 24 Trnava, Slovakia;
juraj.halanda@stuba.sk (J.H.); dusan.vana@stuba.sk (D.V.)
* Correspondence: viera.zatkalikova@fstroj.uniza.sk; Tel.: +421-41-513-2610
Abstract: Plasma immersion ion implantation (PIII) of nitrogen is low-temperature surface tech-
nology which enables the improvement of tribological properties without a deterioration of the
corrosion behavior of austenitic stainless steels. In this paper the corrosion properties of PIII-treated
AISI 316L stainless steel surfaces are evaluated by electrochemical impedance spectroscopy (EIS),
potentiodynamic polarization (PP) and exposure immersion tests (all carried out in the 0.9 wt. % NaCl
solution at 37 ± 0.5 ◦ C) and compared with a non-treated surface. Results of the three performed
independent corrosion tests consistently confirmed a significant increase in the corrosion resistance
after two doses of PIII nitriding.
Keywords: plasma immersion ion implantation of nitrogen; austenitic stainless steel; corrosion
resistance; potentiodynamic polarization; electrochemical impedance spectroscopy
1. Introduction
Austenitic stainless steels are widely used biomaterials owing to their high biocom-
patibility and corrosion resistance. Their current study mostly aims to further improve
their mechanical properties, wear and local corrosion resistance [1–4].
Plasma nitriding process is one of the methods for the thermochemical treatment of
austenitic stainless steels to improve the tribological properties of their surfaces. Conven-
tional plasma nitriding performed at the temperatures of above 500 ◦ C ensures a high
resistance to wear, however, the precipitation of chromium nitride causes a depletion of
chromium in the solid solution and this leads to a reduction in the corrosion resistance. Un-
like this technology the plasma immersion ion implantation of nitrogen (PIII) is performed
at temperatures below 400 ◦ C and it enables the thermochemical surface treatment with a
marked increase of hardness and wear resistance without a deterioration of the corrosion
behaviour of stainless steel [1,2,5–7]. According to numerous authors [1,5–14], so-called
expanded austenite is the phase formed in the N-modified layer under low-temperature
conditions and responsible for the improved properties of such treated stainless steels.
According to the authors of [10], expanded austenite is a crystalline cubic phase with
considerably expanded austenitic lattice which may contain precipitates of different size
and quantity depending on the nitriding temperature used.
PIII technology is based on immersion of the specimen in a plasma and applying
negative high-voltage pulses to it. Positively charged ions are extracted from the plasma
through the plasma sheath and they are implanted on the whole surface at the same time
for reduction of the process time for large pieces and for decreasing the costs [2]. PIII allows
https://www.mdpi.com/journal/materials
 lows one to obtain a higher current density of ions with significantly shorter impl
times and it is also applicable for workpieces with complicated surface shapes [1
Some authors have studied the corrosion resistance of PIII nitrided stainless s
Materials 2021, 14, 6790 faces and found improved pitting corrosion resistance in variously concentrated 2 of 10

environments [1,8,11–13]. In contrast, other authors [7] reported different results

304 stainless steel in 1 wt. % NaCl solution (PIII treated at 300–380 °C).
one to Regarding
obtain a higher current density
biomedical of ions with the
applications, significantly
authorsshorter
of [11]implantation
recommend timeslow-tem
and it is also applicable for workpieces with complicated surface shapes [15].
nitriding for improvement of tribological and corrosion properties of 316L stainl
Some authors have studied the corrosion resistance of PIII nitrided stainless steel
implants
surfaces andand
found for the prevention
improved of metal
pitting corrosion release
resistance as well. concentrated
in variously The corrosion resistance
chloride
was recorded
environments in aerated
[1,8,11–13]. phosphate-buffered
In contrast, saline solution
other authors [7] reported by PP
different results formeasureme
AISI
304 stainless steel in 1 wt. % NaCl solution (PIII treated at 300–380 ◦ C).
Similarly, the authors of [16] confirmed an increase of the pitting corrosion resis
Regarding biomedical applications, the authors of [11] recommend low-temperature
nitride-coated AISI 316L coronary stents, indicated by PP method and long-term
nitriding for improvement of tribological and corrosion properties of 316L stainless steel
implants and for thein
sion (6 months) simulated
prevention bodyrelease
of metal fluidasatwell.
37 ±The1 °C.
corrosion resistance increase
According
was recorded to onephosphate-buffered
in aerated study [1], the higher salineresistance
solution byto PPpitting after PIII
measurements nitriding
[11].
316LVMthe
Similarly, stainless
authors of steel
[16](by PP in 3.5
confirmed wt. % NaCl
an increase of the solution) can beresistance
pitting corrosion explained of by an
nitride-coated AISI 316L coronary stents, indicated by PP method
of the pitting resistance equivalent number (PREN = wt. % Cr + 3.3 × wt. % Mo + and long-term immersion
(6 months) in simulated body fluid at 37 ± 1 ◦ C.
% N) in the surface film. The authors also confirmed a close relation between PR
According to one study [1], the higher resistance to pitting after PIII nitriding of AISI
the pitting
316LVM potential.
stainless steel (by PP in 3.5 wt. % NaCl solution) can be explained by an increase of the
pittingThe objective
resistance of the
equivalent presented
number (PREN paper
= wt. % isCr to compare
+ 3.3 × wt. % Mo the+ corrosion
16 × wt. % N) resistanc
in the surface
nitrided AISI film.
316L Thestainless
authors alsosteelconfirmed
surfacesa withclose that
relation between
of an originalPREN and the
non-treated (as r
pitting potential.
surface. The evaluation is based on three independent test methods: electrochem
The objective of the presented paper is to compare the corrosion resistance of PIII
pedance
nitrided AISIspectroscopy (EIS),
316L stainless steel potentiodynamic
surfaces polarization
with that of an original and (as
non-treated exposure
received)immers
all carried
surface. The out in a 0.9iswt.
evaluation based% NaCl
on threesolution at thetest
independent temperature of 37 ± 0.5 °C for sim
methods: electrochemical
of the internal environment of a human body. The nitrided surfaces were
impedance spectroscopy (EIS), potentiodynamic polarization and exposure immersion test, also ch
all carried out in a 0.9 wt. % NaCl solution at the temperature of 37 ± 0.5 ◦ C for simulation
ized by SEM and EDX analysis.
of the internal environment of a human body. The nitrided surfaces were also characterized
by SEM and EDX analysis.
2. Materials and Methods
2. Materials and Methods
The experimental material AISI 316L is Cr-Ni-Mo austenitic stainless steel (w
The experimental material AISI 316L is Cr-Ni-Mo austenitic stainless steel (wt. %:
16.97, Ni 14.75, Mo 2.50, Mn 1.76, C 0.03, Si 0.49, Cu 0.15, Fe balance) purchase
Cr 16.97, Ni 14.75, Mo 2.50, Mn 1.76, C 0.03, Si 0.49, Cu 0.15, Fe balance) purchased in
form of rectangular
the form of specimens
rectangular specimens 1515
mm mm× 40× 40
mmmm × 2 ×mm 2 mm (BEZNOSKA
(BEZNOSKA SlovakiaSlovakia
Ltd., Ltd.
Bystrica,
Banská Skovakia).
Bystrica, ItsIts
Skovakia). microstructure (Figure
microstructure (Figure 1) is1)formed
is formed by polyhedral
by polyhedral austeniticaustenit
with with
grains numerous
numerous twins,
twins,which
which could
could bebecreated
created by annealing
by annealing or by rolling.
or by rolling.

Figure
Figure 1. 1. Microstructure
Microstructure of316L
of AISI AISIstainless
316L stainless steel, longitudinal
steel, longitudinal section
section (Kallings (Kallings
2 etch.). 2 etch.

PIII nitriding of experimental specimens was performed in the specialized

tory of Plasma Technologies in the Advanced Technologies Research Institute
Materials 2021, 14, 6790 3

Materials 2021, 14, 6790 3 of 10

University of Technology Bratislava, Faculty of Materials Science and Technolog

Trnava, Slovakia).
Prior
PIII to nitriding,
nitriding the surface
of experimental of the
specimens wasspecimens
performed in was
the not mechanically
specialized or chemi
Laboratory
of Plasma Technologies in the Advanced Technologies Research Institute
treated and only degreased with ethanol. The specimens were placed on a holder (Slovak University
of Technology Bratislava, Faculty of Materials Science and Technology in Trnava, Slovakia).
nected to a high voltage power supply and electrically isolated from the chamber
Prior to nitriding, the surface of the specimens was not mechanically or chemical-ly
The nitriding took place in two stages. During the first stage, the same dose of nitrog
treated and only degreased with ethanol. The specimens were placed on a holder con-
× 1017 at/cm
nected
2) was used in all samples. In the second stage a half of specimens was nitr
to a high voltage power supply and electrically isolated from the chamber wall.
by one
The moretook
nitriding dose of the
place in twonitrogen (5 × 10the
stages.During 17 at/cm2) at the same nitriding conditions.
first stage, the same dose of nitrogen
(5 17
× 10 wasat/cm 2
result two)types
was used in all samples.
of nitrided In the
surfaces: withsecond stage a half
one applied doseof of
specimens was
nitrogen (1N) and
nitrided by one more dose of the nitrogen (5 × 10 17 at/cm2 ) at the same nitriding conditions.
two applied doses (2N). An overview of the tested surfaces and specimen designa
The result was two types of nitrided surfaces: with one applied dose of nitrogen (1N) and
for the experiments is given in Table 1.
with two applied doses (2N). An overview of the tested surfaces and specimen designations
for the experiments is given in Table 1.
Table 1. Overview of tested surfaces.
Table 1. Overview of tested surfaces.
Type of Surface Specimen Designation
PIII nitridedTypeby one dose (5 × 1017 at/cm2)
of Surface 1N
Specimen Designation
PIIIPIII
nitrided
nitridedby
bytwo doses
one dose (5 (2 × 517 ×at/cm
× 10 1017 at/cm
2) 2)
1N 2N
PIII nitrided byOriginal
two dosesnon-treated
(2 × 5 × 1017 at/cm2 ) 2N as received
Original non-treated as received
The size of the implanted doses was chosen according to the recommendations o
The size
authors [1] of
andthe[5].
implanted
Nitrogendoses was chosen
plasma was according
generated to by
the arecommendations
radio frequency of discharge
the
authors [1] and [5]. Nitrogen plasma was generated by a radio frequency
a power of 500 W at a chamber pressure of 0.3 Pa. To improve the processing homogen discharge with a
power of 500 W at a chamber pressure of 0.3 Pa. To improve the processing homogeneity
the samples were rotated (10 rpm) during the process. The one dose application of n
the samples were rotated (10 rpm) during the process. The one dose application of nitrogen
gen lasted
lasted approximately
approximately 5 h. The5 pulsed
h. The accelerating
pulsed accelerating
voltage usedvoltage
was 20 used was to
kV (due 20the
kV (due t
technical dispositions of the device) with a frequency of 150 Hz and a pulse length of 15 µs.length
technical dispositions of the device) with a frequency of 150 Hz and a pulse
µs. Rutherford
The The Rutherford Back Scattering
Back Scattering (RBS) method(RBS)wasmethod was used
used to determine thetoexact
determine
implanted the exac
nitrogen dose (Figures 2 and 3).
planted nitrogen dose (Figures 2 and 3).
According
According to the
to height of the nitrogen
the height peaks on RBS
of the nitrogen curves
peaks on (evaluated
RBS curves by the SIM-
(evaluated by
NRA software) the lower implanted dose (1N) was in fact 2.7 × 1017 at/cm217(the set-2
SIMNRA software) the lower implanted dose (1N) was in fact 2.7 × 10 at/cm (the se
ting on the device was 5 × 1017 at/cm2 ). The higher implanted dose (2N) was set to
1on
× the
1018device
at/cm2 was 5 × means
1017 at/cm
2 × 5).×
2 The17
(which 10 higher
at/cmimplanted dose
2 ) and in fact 4.2 ×(2N)
1017was set2 to
at/cm was1 × 1018 at
(which means
measured. 2 × 5 × 1017between
The differences at/cm2)theandsetinand
factactual
4.2 ×dose
1017 at/cm 2 was measured. The differe
were caused by the so-called
between
dust theeffect.
removal set and actual dose were caused by the so-called dust removal effect.

Figure2.2.Measured
Figure Measuredandand evaluated
evaluated RBS spectrum
RBS spectrum of 1N specimen,
of 1N specimen, measured N measured N17dose
dose 2.7 × 10 at/cm2.7
2 . × 1017 a
 Materials 2021, 14, 6790 4 of 10
Materials 2021, 14, 6790 4 of 10

Figure3.3.Measured
Figure Measuredand
and evaluated
evaluated RBSRBS spectrum
spectrum of 2Nofspecimen,
2N specimen, measured
measured N dose N
4.2dose
× 104.2 × 10 2at/cm
17 at/cm .
17 2.

For
Formore
moredetailed
detailedcharacterization, the nitrided
characterization, specimen
the nitrided surfacessurfaces
specimen were displayed and
were displayed
EDX
and analysed
EDX analysedby a Vega
by scanning electron microscope
a Vega scanning (SEM, Tescan,(SEM,
electron microscope Brno, Czech
Tescan, Republic).
Brno, Czech
The temperature of 37 ± 0.5 ◦ C and 0.9 wt. % sodium chloride solution for simulation
Republic).
the internal environment
The temperature of of
37the human
± 0.5 °C andbody
0.9 was
wt. %used as thechloride
sodium environment for corrosion
solution for simulation
tests. The electrochemical corrosion tests (EIS and potentiodynamic polarization) were
the internal environment of the human body was used as the environment for corrosion
performed in the conventional three-electrode cell system with a calomel reference electrode
tests. The electrochemical corrosion tests (EIS and potentiodynamic polarization) were
(SCE) and a platinum auxiliary electrode (Pt) using a BioLogic corrosion measuring system
aperformed
with PGZ 100 in the conventional
measuring three-electrode
unit (BioLogic, cell system
Seyssinet-Pariset, withThe
France). a calomel
time forreference
potential elec-
trode (SCE) between
stabilization and a platinum
the specimenauxiliary electrode
and the (Pt)was
electrolyte usingset atoBioLogic corrosion
10 min. The exposedmeasuring
area
system a with PGZ
of a specimen was 1 cm . 100 2 measuring unit (BioLogic, Seyssinet-Pariset, France). The time for
potential stabilization
Electrochemical between spectroscopy
impedance the specimenmeasurements
and the electrolyte was set at
were recorded to the
10 min.
cor- The
exposed
rosion area of over
potential a specimen was 1range
a frequency cm . from 100 KHz to 5 mHz. Results of EIS mea-
2

Electrochemical
surements were displayed impedance
as Nyquistspectroscopy measurements
curves plotted in coordinates wereofrecorded
real andatimagi-
the corro-
nary impedance components. The polarization resistance (R ) values
sion potential over a frequency range from 100 KHz to 5pmHz. Results of EIS measure- were obtained by
the analysis of the representative Nyquist curves using the EC-LAB
ments were displayed as Nyquist curves plotted in coordinates of real and imaginary im- software (BioLogic,
Seyssinet-Pariset,
pedance components. France).The polarization resistance (Rp) values were obtained by the analy-
The potentiodynamic
sis of the representative Nyquist polarization curves
curves were
using therecorded
EC-LABatsoftwarethe sweep(BioLogic,
rate of 1 mV/s,
Seyssinet-
a potential scan range was applied between −0.3 and 1.2 V vs. open circuit potential
Pariset, France).
(OCP) [17,18]. For both EIS and PP measurements at least three experiment repeats were
The potentiodynamic polarization curves were recorded at the sweep rate of 1 mV/s,
carried out for each type of surface.
a potential scan range
For 50-days was applied
exposure betweentests
immersion −0.3 and 1.2 V vs. of
specimens open circuit potential
rectangular shape(OCP)
[17,18]. For both EIS and PP measurements at least three experiment
(15 mm × 40 mm × 1.5 mm) were degreased by ethanol and weighted out with accuracy repeats were carried
(out for each
±0.00001 g). type of surface.
A group of three parallel specimens was tested for each type of surface. After
exposure the specimens wereimmersion
For 50-days exposure tests specimens
carefully brushed, washed with of rectangular
demineralized shape (15
water, mm × 40
freely
mm ×and
dried 1.5 weighed
mm) were degreased
again [18]. by ethanol and weighted out with accuracy (± 0.00001 g).
A group of three parallel specimens was tested for each type of surface. After exposure
3.
theResults and Discussion
specimens were carefully brushed, washed with demineralized water, freely dried and
The nitrided
weighed surfaces (1N and 2N) observed by SEM and, also EDX maps expressing
again [18].
N and Fe distribution are shown in Figures 4 and 5. EDX surface analysis revealed an
uneven distribution
3. Results of nitrogen on the surface layer of the tested stainless steel in the case
and Discussion
of both 1N and 2N specimens. The same as described in studies with similar conditions of
The nitrided surfaces (1N and 2N) observed by SEM and, also EDX maps expressing
PIII nitriding, nitrogen may be present in the form of expanded austenite [1,2,5,6,8] which
N and Fe to
is difficult distribution
identify andare
it isshown in Figures
observable using a4transmission
and 5. EDXelectron
surfacemicroscope
analysis revealed
[1,5]. an
uneven distribution of nitrogen on the surface layer of the tested stainless steel in the case
of both 1N and 2N specimens. The same as described in studies with similar conditions of
PIII nitriding, nitrogen may be present in the form of expanded austenite [1,2,5,6,8] which
is difficult to identify and it is observable using a transmission electron microscope [1,5].
Materials 2021, 14, 6790 5 of 10
Materials 2021, 14, 6790 5 of 10
Materials 2021, 14, 6790 5 of 10

(a)
(a) (b)
(b)
Figure4.
Figure 1Nnitrided
4.1N nitridedspecimen
specimensurface
surface(a)
(a)SEM,
SEM,(b)
(b)EDX
EDX map—N
map—N and
and Fe
Fe distribution.
distribution.
Figure 4. 1N nitrided specimen surface (a) SEM, (b) EDX map—N and Fe distribution.

(a)
(a) (b)
(b)
Figure 5.
Figure 5. 2N nitrided
nitrided specimen surface
surface (a) SEM,
SEM, (b) EDX
EDX map—N and
and Fe distribution.
distribution.
Figure 5.2N
2N nitridedspecimen
specimen surface(a)
(a) SEM,(b)
(b) EDXmap—N
map—N andFe
Fe distribution.

3.1. EIS
3.1. EIS Test
3.1. EISTest
Test
The measured
The measured impedance spectra spectra werewere simple
simple and and therefore
therefore aa single
single loop
loop circuit
circuit con-
con-
The measuredimpedance impedance spectra were simple and therefore a single loop circuit
sisting of
sisting of electrolyte resistance
resistance (R ), polarization
(RΩΩ), polarization resistance
resistance (R (Rpp)) and
and CPECPE element con- con-
consistingelectrolyte
of electrolyte resistance (RΩ ), polarization resistance (Rp ) and element
CPE element
nected
nected to the
to the circuit
circuit instead
instead of
of ofthe
thethecapacitance
capacitance (R Ω + CPE/Rp), was used for the Nyquist
connected to the circuit instead capacitance(R(R Ω ++ CPE/Rp), was used for the Nyquist
Ω CPE/Rp ), was used for the Nyquist
curves evaluation
curves evaluation [19–21].
[19–21]. The The CPE
CPE element
element was was used
used to simulate
simulate inhomogeneities of of the
curves evaluation [19–21]. The CPE element was usedto to simulateinhomogeneities
inhomogeneities ofthe the
surface
surface layer [21]. The Nyquist curves for the tested surfaces are shown in Figure 6, values
surfacelayer
layer[21].
[21].The
TheNyquist
Nyquistcurvescurvesfor forthe
thetested
testedsurfaces
surfacesare areshown
shownin inFigure
Figure6,6,values
values
of the
of the EIS parameters
parameters calculated by by the EC-LAB
EC-LAB software are are listed in in Table 2. 2.
of theEIS
EIS parameterscalculated
calculated bythe the EC-LABsoftware software arelistedlisted in Table
Table 2.
The polarization
The polarization resistance
resistance (Rpp)) enables
enables one one to to assess
assess thethe passive
passive filmfilm quality:
quality: aa
The resistance (R(R p ) enables one to assess the passive film quality: a higher
higher
higher R p value points to a higher quality. As can be seen, the PIII nitriding brought a
Rp value
Rp value pointspoints to a higher
to a higher quality. quality.
As canAsbecan seen,be the
seen, thenitriding
PIII PIII nitriding
brought brought
a sharp a
sharp
sharp increase
increase
increase of Rp ofof Rpp values
R
values values
of both of1N
of both
bothand 1N
1N 2Nand
and 2N surfaces.
2N
surfaces. surfaces.
Two-dose Two-dose
Two-dose
nitriding nitriding
nitriding
has been hasshown
has been
been
shown
shown to be
to be particularly
particularly
to be particularly effective:effective:
effective:
Rp value RRpp value
value
for 2N for
for 2N specimen
2N
specimenspecimen was more
was
was more more than
than than twice
twicetwice
higher higher
higher
than
than
than for
for 1N. 1N.
for 1N.
High High
High quality
quality
quality passive
passive
passive filmfilm
film of
of of PIII nitrided
PIIInitrided
PIII specimens
nitridedspecimens
specimensmay may
may be be connected
be connected to to the
to the
the
molybdenium
molybdeniumpresent
molybdenium present
presentin ininthe
the
thetested
tested
tested AISI
AISIAISI316L
316L316Lstainless
stainless
stainless steel
steel (2.5(2.5
steel
(2.5 wt. wt.
wt. %). According
%). According
%). According to sev-
to sev-
to
eral
eral authors
several
authors [12,22,23]
authors Mo atoms
[12,22,23]
[12,22,23] Mo atoms
Mo atomstend to
tend to stabilize
tend the expanded
to stabilize
stabilize the expanded
the expandedaustenite
austenite structure
austenite
structure by at-
structure
by at-
tracting
tracting nitrogenium
by attracting atoms around
nitrogenium
nitrogenium atoms aroundaround
atoms themselves
themselves and this
themselves
and thisand
leads
this
leads to leads
to the prevention
the prevention of chro-
to the prevention
of chro-
mium
mium nitride
of chromium precipitation. Two-dose
nitride precipitation.
nitride precipitation. Two-doseTwo-dose nitriding could
nitriding nitriding enhance
could enhance these
couldthese
enhance processes, resulting
these processes,
processes, resulting
in a high
resulting resistance
in a high of a thus-treated
resistance of a
in a high resistance of a thus-treated surface. surface.
thus-treated surface.
Materials 2021, 14, 6790 6 of 10
Materials 2021, 14, 6790 6 of 10

700000

600000

500000

400000 2N
1N
300000 as received
as received F
200000
1N F
100000 2N F
-ZIm [Ω.cm2]

0
0 200000 400000 600000 800000
ZRe [Ω.cm2]
Figure6.
Figure 6. Nyquist
Nyquist curves
curves for
for tested
tested surfaces
surfaces(fitted
(fittedcurves
curvesare
are“F”
“F”marked).
marked).

Table 2. Values of EIS parameters.

Table 2. Values of EIS parameters.
Specimen Designation (Type of Polarization Resistance Rp Electrolyte Resistance RΩ
Specimen Designation Polarization Resistance Rp Electrolyte Resistance RΩ
Surface) (kΩ.cm2) (kΩ.cm2)
(Type of Surface) (kΩ.cm2 ) (kΩ.cm2 )
As received 27.5 ± 0.3 0.054 ± 0.002
As received
1N 587.1±±0.3
27.5 1.5 0.040±± 0.002
0.054 0.001
1N
2N 1256.0±±1.5
587.1 1.9 0.057±± 0.001
0.040 0.002
2N 1256.0 ± 1.9 0.057 ± 0.002

3.2. Potentiodynamic Polarization Test

3.2. Potentiodynamic Polarization Test
As shown in Figure 7, the shape of polarization curves is typical for passivating met-
As shown
als (passive in Figure
anodic 7, the shape
branches of polarization
reflecting the controlcurves
of theisanodic
typicaldissolution
for passivating
rate metals
by the
(passive anodic branches reflecting the control of the anodic dissolution rate by
passive current density) [24] and therefore the corrosion potential (Ecorr) values werethe passive
de-
current density) [24] and therefore the corrosion potential (E corr ) values
termined directly from the PP curves (Tafel extrapolation was not applicable). were determined
directly from the PP curves (Tafel extrapolation was not applicable).
The pitting potential (Ep ) values, that denote the disruption of the passive surface
film and the onset of the stable pit growth, were determined as the potentials of a sudden
permanent increase in current density after reaching the passivity state. The values of both
above mentioned PP parameters are listed in Table 3.

Table 3. Values of PP parameters.

Specimen Designation Corrosion Potential Ecorr Pitting Potential Ep

(Type of Surface) (V vs. SCE) (V vs. SCE)
as received −0.126 ± 0.02 0.449 ± 0.03
1N 0.017 ± 0.03 0.330 ± 0.04
2N 0.059 ± 0.02 0.567 ± 0.03
 Materials
Materials 2021, 14,14,
2021, 6790
6790 7 of7 of
1010

0
-0.6 -0.4 -0.2 0 0.2 0.4 0.6 0.8 1 1.2
-1

log i (A/cm2) -2

-3

-4
as received
-5 1N
2N
-6

-7

-8
E vs SCE (V)
Figure 7. Potentiodynamic polarization curves for tested surfaces.
Figure 7. Potentiodynamic polarization curves for tested surfaces.
According to the Ecorr values, PIII nitriding caused a marked increase in the thermody-
namic Thestability
pitting of the tested
potential (Epsurfaces,
) values,and thatthe highest
denote theEcorr value was
disruption ofreached for 2N
the passive surface
surface
(0.059 V vs. SCE). An E increase of about 0.1 V between
film and the onset of the stable pit growth, were determined as the potentials of a sudden
corr non-treated and PIII nitride
surfaces (AISI 316L in 5 wt. % NaCl solution) was also recorded
permanent increase in current density after reaching the passivity state. The values of both by other authors [12].
Olzon-Dionisio et al. [8] observed
above mentioned PP parameters are listed in Table 3. an E corr difference of 0.15 V for the same surface (AISI
316L in 5 wt. % NaCl solution) after using the same nitriding temperature.
Table 3.Regarding
Values of PP theparameters.
evaluation of the pitting corrosion resistance expressed by the Ep value
(0.330 V vs. SCE), the single dose nitriding (1N) probably did not provide a sufficiently
Specimen
uniform Designation
passive film. Ep value Corrosion
after 2N Potential Ecorris significantly
nitriding Pitting Potential Ep
higher (0.567 vs. SCE).
(Type of Surface) (V vs SCE)
A similar dependence of Ep on the PIII nitriding time was observed in the study [11], but (V vs SCE)
not under as received
the same PP experiment−0.126 ± 0.02 (different solution
conditions 0.449and
± 0.03
temperature). The
1N 0.017 ± 0.03 0.330 ± 0.04
best pitting corrosion resistance of the 2N surface could be related to the role of nitrogen
2N 0.059 ± 0.02 0.567 ± 0.03
in the corrosion pits repassivation process. According to the authors of [13] nitrogen is
responsible for pH increase which facilitates the pits’ repassivation, because of its reduction
(from According
N0 to N−toIIIthe) byEbinding
corr values, PIII nitriding
of protons H+ intocaused ammonium a marked increase
cations (NH4 +in). the thermo-
Subsequently,
dynamic
NH4 + cations stabilitycanof undergo
the testedoxidation
surfaces, to andNO the− highest Ecorr value was reached for 2N
2 anions [13] which can contribute to pit
surface (0.059 V vs SCE). An E corr increase of about 0.1 V between non-treated and PIII
repassivation [13]. These processes could be affected by the content of nitrogen in the steel
nitride
surface surfaces
film. (AISI 316L in 5 wt. % NaCl solution) was also recorded by other authors
[12]. Olzon-Dionisio et al. [8] observed an Ecorr difference of 0.15 V for the same surface
(AISI
3.3. 316L
Exposurein 5 Immersion
wt. % NaCl solution) after using the same nitriding temperature.
Test
Regarding
The tested the evaluation
stainless steelofsurfaces
the pitting
before corrosion
and afterresistance
50-daysexpressed by theconditions
exposure under Ep value
(0.330 V vs SCE),
simulating the single
the internal humandosebodynitriding (1N) probably
environment (0.9 wt.did % not
NaCl provide
solutiona sufficiently
at 37 ◦ C) are
uniform
shownpassive in Figure film.
8. EThe
p value aftercorrosion
average 2N nitriding is calculated
rates significantly higher
from the (0.567 vs SCE).
mass losses of A
the
specimens (mass loss per unit area per unit time, g/(m day)) are listed in Table 4. not
similar dependence of E p on the PIII nitriding time was observed
2 in the study [11], but
under the After same PP experiment
performing conditions
the exposure tests,(different solution
all three types and temperature).
of surfaces (as received, The1N,best
2N)
pitting
showed corrosion
only veryresistance of the 2N surface
small differences could be
in appearance related to
compared tothe
therole
stateofbefore.
nitrogen in the
According
corrosion
to the values pits repassivation process.rates,
of average corrosion According to the
the pitting authors
seemed toof
be[13]
most nitrogen
pronouncedis respon-
on the
sible
surfacefor pH increase
of the whichspecimens,
as received facilitates where
the pits’ repassivation,
is probably relatedbecause of its
to the sites of reduction
mechanical
(from
damage N0 towithN−III)an
byimperfect
binding ofpassive
protonsfilm. H+ into ammonium
Pitting corrosion cations (NH4+). Subsequently,
of austenitic stainless steels
NH + cations can undergo oxidation to NO2− anions [13] which can contribute to pit re-
initiated in this way has been documented by several authors, e.g., [18,21,25]. The average
4

passivation
corrosion [13]. ratesThese
values processes
of 1N and could2Nbe affected by
specimens arethe content
less of nitrogen
than half compared in the
to steel
the as
surface
received film.one. This corresponds with the results of both electrochemical corrosion tests
and points to the abovementioned positive role of nitrogen in the pit repassivation process
(Section 3.2). Recorded low corrosion rates also indicate a potentially negligible leakage of
Materials 2021, 14, 6790 8 of 10

Materials 2021, 14, 6790 8 of 10

3.3. Exposure Immersion Test
The tested stainless steel surfaces before and after 50-days exposure under conditions
simulating the internal human body environment (0.9 wt. % NaCl solution at 37 °C) are
harmful
shown substances
in Figure 8. Theinto the human
average body rates
corrosion [26–30] and suggest
calculated froma the
highmass
biocompatibility
losses of the of
PIII nitrided surfaces [11].
specimens (mass loss per unit area per unit time, g/(m day)) are listed in Table 4.
2

(a) (b)

(c) (d)

(e) (f)
Figure 8. The
Figure tested
8. The stainless
tested steel
stainless surfaces
steel before
surfaces and
before after
and 50-days
after exposure
50-days (optical
exposure microscope):
(optical microscope):
as as
received surface (a) before, (b) after; 1N surface (c) before, (d) after; 2N surface (e) before, (f) (f)
received surface (a) before, (b) after; 1N surface (c) before, (d) after; 2N surface (e) before, after.
after.

Table 4. Average corrosion rates calculated from mass losses during the exposure test.
Table 4. Average corrosion rates calculated from mass losses during the exposure test.
Specimen Designation Average Corrosion Rate
Specimen Designation Average Corrosion Rate
(Type of Surface) (g/(m22day))
(Type of Surface) (g/(m day))
As received 0.00094 ± 0.93%
As received
1N 0.00094 ±±0.81%
0.00038 0.93%
1N
2N 0.00038 ± 0.81%
0.00033 ± 0.84%
2N 0.00033 ± 0.84%

After performing the exposure tests, all three types of surfaces (as received, 1N, 2N)
4. Conclusions
showed only very small differences in appearance compared to the state before. Accord-
On the bases
ing to the values of the performed
of average corrosion experiments the following
rates, the pitting seemed tocan be concluded:
be most pronounced on
the• surface of the as received specimens, where is probably related to the
Surface EDX analysis of 1N and 2N specimens revealed uneven distribution sites of mechan-
of nitrogen.
ical• damage with an imperfect passive film. Pitting corrosion of austenitic stainless
According to the Rp values of 1N and 2N surfaces, PIII nitriding brought about steels a
significant increase of the passive film quality. Two-dose nitriding resulted in a more
than two-fold higher Rp than recorded for 1N.
Materials 2021, 14, 6790 9 of 10

• The results of the PP test showed that the surface after two-dose PIII nitriding (2N)
appeared to be the most resistant to pitting (this was shown by the highest Ecorr and
Ep potential values). This is probably associated with a positive role of nitrogen in the
repassivation process.
• Average corrosion rates calculated from mass losses during exposure immersion test
confirmed the high corrosion resistance of both 1N and 2N surfaces.
According to the obtained experiment results, PIII nitriding appears to be a suitable
method for the surface treatment of austenitic stainless steels implants. However, before
actual biomedical applications deeper studies of the relations between the surface rough-
ness before PIII nitriding and the final biocompatibility (including the corrosion resistance
and resistance to the biofilm formation) would be beneficial.

Author Contributions: Conceptualization, V.Z.; methodology, V.Z., J.H., D.V. and M.Š.; software,
M.Š.; validation, J.H. and L.M.; investigation, V.Z., J.H. and D.V.; resources, M.U. and L.M.;
writing—original draft preparation, V.Z.; writing—review and editing, V.Z.; visualization, M.U.;
supervision, L.K.; project administration, L.K. All authors have read and agreed to the published
version of the manuscript.
Funding: The research was supported partially by Scientific Grant Agency of Ministry of Education,
Science and Sport of Slovak Republic and Slovak Academy of Sciences grants KEGA No. 013ŽU-
4/2019 and VEGA No. 1/0134/20 and by Project to support young researchers at UNIZA, ID of
project 12715—project leader Ing. Lenka Kuchariková.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Data sharing is not applicable to this article.
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Saravanan, P.; Raja, V.S.; Mukherjee, S. Effect of plasma immersion ion implantation of nitrogen on the wear and corrosion
behavior of 316LVM stainless steel. Surf. Coat. Technol. 2007, 201, 8131–8135. [CrossRef]
2. Mändl, S.; Günzel, R.; Richter, E.; Möller, W. Nitriding of austenitic stainless steel using plasma immersion ion implantation. Surf.
Coat. Technol. 1998, 100–101, 372–376. [CrossRef]
3. Khattak, H.S.; Raj, B. Corrosion of Austenitic Stainless Steels, Mechanism, Mitigation and Monitoring; ASM International: Novelty, OH,
USA, 2002; pp. 9–27.
4. Lipińsky, T. Investigation of corrosion rate of X55CrMo14 stainless steel at 65% nitrate acid at 348 K. Prod. Eng. Arch. 2021, 27,
108–111. [CrossRef]
5. Collins, G.A.; Hutchings, R.; Short, K.T.; Tendys, J.; Li, X.; Samandi, M. Nitriding of austenitic stainless steel by plasma immersion
ion implantation. Surf. Coat. Technol. 1995, 74–75, 417–424. [CrossRef]
6. Blawert, C.; Weisheit, A.; Mordike, B.L.; Knoop, F.M. Plasma immersion ion implantation of stainless steel: Austenitic stainless
steel in comparison to austenitic-ferritic stainless steel. Surf. Coat. Technol. 1996, 85, 15–27. [CrossRef]
7. Mukherjee, S.; Raole, P.M.; Kumar, A.; Chattoraj, I.; Rao, K.R.M.; Manna, I. Studies on low-energy nitrogen plasma immersion ion
implantation on austenitic stainless steel and Cu-strengthened HSLA-100 steel. Surf. Coat. Technol. 2004, 186, 282–286. [CrossRef]
8. Olzon-Dionysio, M.; Olzon-Dionysio, D.; Campos, M.; Takemitsu Shigeyosi, W.; de Souza, S.D.; de Souza, S. Corrosion resistance
of AISI 316L plasma nitrided at different temperatures and times. Hyperfine Interact. 2019, 240, 26. [CrossRef]
9. Fewell, M.P.; Mitchell, D.R.G.; Priest, J.M.; Shortb, K.T.; Collins, G.A. The nature of expanded austenite. Surf. Coat. Technol. 2000,
131, 300–306. [CrossRef]
10. Latella, B.A.; Short, K.T. Tension-driven cracking of an expanded austenite layer. J. Mater. Sci. 2004, 39, 4321–4324. [CrossRef]
11. Martinesi, M.; Bruni, S.; Stio, M.; Treves, C.; Bacci, T.; Borgioli, F. Biocompatibility evaluation of surface-treated AISI 316L
austenitic stainless steel in human cell cultures. J. Biomed. Mater. Res. A 2007, 80, 131–145. [CrossRef]
12. Borgioli, F.; Galvanetto, E.; Bacci, E. Low temperature nitriding of AISI 300 and 200 series austenitic stainless steels. Vacuum 2016,
127, 51–60. [CrossRef]
13. Flis-Kabulska, I.; Sunb, Y.; Flis, J. Monitoring the near-surface pH to probe the role of nitrogen in corrosion behaviour of
low-temperature plasma nitrided 316L stainless steel. Electrochim. Acta 2013, 104, 208–215. [CrossRef]
14. Adachi, S.; Egawa, M.; Yamaguchi, T.; Ueda, N. Low-Temperature Plasma Nitriding for Austenitic Stainless Steel Layers with
Various Nickel Contents Fabricated via Direct Laser Metal Deposition. Coatings 2020, 10, 365. [CrossRef]
15. Gupta, D. Plasma Immersion Ion Implantation (PIII) Process-Physics AND Technology. Int. J. Adv. Technol. 2011, 2, 471–490.
Materials 2021, 14, 6790 10 of 10

16. Liu, C.L.; Chu, P.K.; Lin, G.Q.; Qi, M. Anti-corrosion characteristics of nitride-coated AISI 316L stainless steel coronary stents.
Surf. Coat. Technol. 2006, 201, 2802–2805. [CrossRef]
17. Kuchariková, L.; Liptáková, T.; Tillová, E.; Kajánek, D.; Schmidová, E. Role of Chemical Composition in Corrosion of Aluminum
Alloys. Metals 2018, 8, 581. [CrossRef]
18. Zatkalíková, V.; Markovičová, L.; Škorvanová, M. Corrosion behaviour of electropolished AISI 316L austenitic biomaterial in
physiological solution. IOP Conf. Ser Mater. Sci. Eng. 2017, 266, 012016. [CrossRef]
19. Zatkalíková, V.; Iwaniak, A.; Markovičová, L.; Uhríčik, M.; Hanusová, P. Corrosion resistance of the chemically treated austenitic
stainless steel in relation to temperature. Przem. Chem. 2020, 99, 844–847. [CrossRef]
20. Brytan, Z.; Niagaj, R.; Reiman, L. Corrosion studies using potentiodynamic and EIS electrochemical techniques of welded lean
duplex stainless steels UNSS82441. Appl. Surf. Sci. 2016, 388, 160–168. [CrossRef]
21. Ghanavati, S.; Shishesaz, M.R.; Farzam, M.; Danaee, I. Effects of Surface Treatment on Corrosion Resistance of 304L and 316L
Stainless Steel Implants in Hank’s Solution. Iran. J. Oil Gas Sci. Technol. 2016, 5, 65–72. [CrossRef]
22. Saravanan, P.; Raja, V.S.; Mukherjee, S. Effect of alloyed molybdenum on corrosion behavior of plasma immersion nitrogen ion
implanted austenitic stainless steel. Corros. Sci. 2013, 74, 106–115. [CrossRef]
23. Egawa, M.; Ueda, N.; Nakata, K.; Tsujikawa, M.; Tanaka, M. Effect of additive alloying element on plasma nitriding and carbuizing
behavior for austenitic stainless steels. Surf. Coat. Technol. 2010, 205, S246–S251. [CrossRef]
24. Bosch, J.; Martin, U.; Aperador, W.; Bastidas, J.M.; Ress, J.; Bastidas, D.M. Corrosion Behavior of High-Mn Austenitic Fe–Mn–Al–
Cr–C Steels in NaCl and NaOH Solutions. Materials 2021, 14, 425. [CrossRef]
25. Szklarska–Smialowska, Z. Pitting and Crevice Corrosion, 1st ed.; NACE International: Houston, TX, USA, 2005; pp. 20–140.
26. Pavlásek, P.; Rybář, J.; Ďuriš, S.; Hučko, B.; Chytil, M.; Furdová, A. Developments and Progress in Non-Contact Eye Tonometer
Calibration. Meas. Sci. Rev. 2020, 20, 171–177. [CrossRef]
27. Chen, Q.; Thouas, G.A. Metallic implant biomaterials. Mat. Sci. Eng. R 2015, 87, 1–57. [CrossRef]
28. Hallab, N.J.; Jacobs, J.J.; Skipor, A.; Black, J.; Mikecz, K.; Galante, J.O. Systemic metal-protein bindingassociated with total joint
replacement arthroplasty. J. Biomed. Mater. Res. 2000, 49, 353–361. [CrossRef]
29. Hanusová, P.; Palček, P.; Uhríčik, M.; Melišík, M. A study of hip joint replacement failure. Mater. Today Proc. 2020, 32 Pt 2, 179–182.
[CrossRef]
30. Kabir, M.A.; Murata, M.; Shakya, M.; Yamada, K.; Akazawa, T. Bio-Absorption of Human Dentin-Derived Biomaterial in Sheep
Critical-Size Iliac Defects. Materials 2021, 14, 223. [CrossRef] [PubMed]